Visible light induced cyclopropanation of dibromomalonates with alkenes via double-SET by photoredox catalysis.

We report herein a visible light induced generation of a carbanion via double-SET and its application in cyclopropanation of alkenes. This new synthetic approach to form cyclopropane derivatives was conducted under mild conditions, using sunlight in open air, showing the features such as environmental benignness and an easy to handle procedure.

[1]  D. MacMillan,et al.  Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis , 2011, Nature.

[2]  Vincenzo Balzani,et al.  Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence , 1988 .

[3]  V. Balzani,et al.  Characterization of the Excited State Properties of Some New Photosensitizers of the Ruthenium (Polypyridine) Family , 1981 .

[4]  Corey R J Stephenson,et al.  Visible light-mediated atom transfer radical addition via oxidative and reductive quenching of photocatalysts. , 2012, Journal of the American Chemical Society.

[5]  C. Paradisi,et al.  Competition between radical and nonradical reactions of halonitrobenzenes in alkaline alcoholic solutions , 1990 .

[6]  Corey R J Stephenson,et al.  Visible light photoredox catalysis: applications in organic synthesis. , 2011, Chemical Society reviews.

[7]  Corey R J Stephenson,et al.  Intermolecular atom transfer radical addition to olefins mediated by oxidative quenching of photoredox catalysts. , 2011, Journal of the American Chemical Society.

[8]  M. Yasuda,et al.  Tris(2,2'-bipyridine)ruthenium(2+)-mediated photoreduction of olefins with 1-benzyl-1,4-dihydronicotinamide: a mechanistic probe for electron-transfer reactions of NAD(P)H-model compounds , 1981 .

[9]  D. MacMillan,et al.  Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. , 2013, Chemical reviews.

[10]  K. Chan,et al.  Triphyrin catalyzed direct C–H arylation of benzene with aryl halides , 2012 .

[11]  Qisong Liu,et al.  Visible-light-promoted C-C bond cleavage: photocatalytic generation of iminium ions and amino radicals. , 2012, Angewandte Chemie.

[12]  John D. Nguyen,et al.  Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions , 2012, Nature Chemistry.

[13]  D. MacMillan,et al.  Photoredox Activation for the Direct &bgr;-Arylation of Ketones and Aldehydes , 2013, Science.

[14]  S. Linic,et al.  Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State , 2013, Science.

[15]  Y. Lan,et al.  Visible-light-mediated decarboxylation/oxidative amidation of α-keto acids with amines under mild reaction conditions using O(2). , 2014, Angewandte Chemie.

[16]  David A. Nicewicz,et al.  Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes , 2008, Science.

[17]  Durga Prasad Hari,et al.  The photocatalyzed Meerwein arylation: classic reaction of aryl diazonium salts in a new light. , 2013, Angewandte Chemie.

[18]  Xiaoqing Xin,et al.  Tandem halogenation/Michael-initiated ring-closing reaction of α,β-unsaturated nitriles and activated methylene compounds: one-pot diastereoselective synthesis of functionalized cyclopropanes. , 2014, Organic & biomolecular chemistry.

[19]  Christopher K Prier,et al.  Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated Serendipity , 2011, Science.

[20]  Eun Jin Cho,et al.  Controlled trifluoromethylation reactions of alkynes through visible-light photoredox catalysis. , 2014, Angewandte Chemie.

[21]  Jagan M. R. Narayanam,et al.  Visible-light-mediated conversion of alcohols to halides. , 2011, Nature chemistry.

[22]  D. Kawai,et al.  Cyclopropanation of electron-deficient alkenes with activated dibromomethylene compounds mediated by lithium iodide or tetrabutylammonium salts , 2009 .

[23]  Jian Wang,et al.  Organocatalytic enantioselective cascade Michael-alkylation reactions: synthesis of chiral cyclopropanes and investigation of unexpected organocatalyzed stereoselective ring opening of cyclopropanes. , 2007, Journal of the American Chemical Society.

[24]  Ying He,et al.  Dual Visible Light Photoredox and Gold-Catalyzed Arylative Ring Expansion , 2014, Journal of the American Chemical Society.

[25]  Melanie S. Sanford,et al.  Room-temperature C-H arylation: merger of Pd-catalyzed C-H functionalization and visible-light photocatalysis. , 2011, Journal of the American Chemical Society.

[26]  Shunichi Fukuzumi,et al.  Tris(bipyridyl)ruthenium(II)-photosensitized reaction of 1-benzyl-1,4-dihydronicotinamide with benzyl bromide , 1984 .

[27]  A. Córdova,et al.  A Simple Organocatalytic Enantioselective Cyclopropanation of α,β‐Unsaturated Aldehydes , 2007 .

[28]  Wen-Jing Xiao,et al.  Visible-light photoredox catalysis. , 2012, Angewandte Chemie.

[29]  Hao Guo,et al.  Amine-catalyzed direct photoarylation of unactivated arenes. , 2014, Chemistry, an Asian journal.

[30]  M. A. Ischay,et al.  Visible light photocatalysis as a greener approach to photochemical synthesis. , 2010, Nature chemistry.

[31]  Yoshihiro Miyake,et al.  Visible-light-mediated utilization of α-aminoalkyl radicals: addition to electron-deficient alkenes using photoredox catalysts. , 2012, Journal of the American Chemical Society.

[32]  J. Sarrazin,et al.  Cyclocondensation reactions from electrogenerated halomalonate carbanions―compared reactivity of bromo and chloro anions and influence of the supporting-electrolyte cation , 1990 .

[33]  Danielle M. Schultz,et al.  Solar Synthesis: Prospects in Visible Light Photocatalysis , 2014, Science.

[34]  Grossi,et al.  Characterization, via ESR spectroscopy, of radical intermediates in the photooxidation of arylcarbinols by ceric ammonium nitrate , 2000, The Journal of organic chemistry.

[35]  Z. Starikova,et al.  Stereoselective electrocatalytic transformation of malonate and alkylidenecyanoacetates into (E)-3-substituted 2-cyanocyclopropane-1,1,2-tricarboxylates , 2006 .

[36]  Jia-Rong Chen,et al.  Homogeneous visible-light photoredox catalysis. , 2013, Angewandte Chemie.

[37]  Guo-Bo Deng,et al.  Tandem cyclizations of 1,6-enynes with arylsulfonyl chlorides by using visible-light photoredox catalysis. , 2013, Angewandte Chemie.

[38]  Kuppuswamy Kalyanasundaram,et al.  Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues , 1982 .

[39]  Danielle M. Schultz,et al.  A Dual-Catalysis Approach to Enantioselective [2 + 2] Photocycloadditions Using Visible Light , 2014, Science.